U.S. patent number 3,855,147 [Application Number 05/257,303] was granted by the patent office on 1974-12-17 for synthetic smectite compositions, their preparation, and their use as thickeners in aqueous systems.
This patent grant is currently assigned to N L Industries, Inc.. Invention is credited to William T. Granquist.
United States Patent |
3,855,147 |
Granquist |
December 17, 1974 |
**Please see images for:
( Certificate of Correction ) ** |
SYNTHETIC SMECTITE COMPOSITIONS, THEIR PREPARATION, AND THEIR USE
AS THICKENERS IN AQUEOUS SYSTEMS
Abstract
A process for preparing novel synthetic smectite compositions
related to saponite plus accessory hydrous magnesia, and the
resulting products. The novel substances have extraordinary
swelling and gelling properties in aqueous solutions, including
strong electrolyte solutions, and have other specific utilities
depending therefrom. The synthetic smectite compositions have the
following formula per unit cell: {[Mg.sub.6 Al.sub.x Si.sub.8.sub.-
x O.sub.20 (OH.sub.4.sub.-a F.sub.a) .sup.x.sup.- XM.sup.Z /z }
+yMg (O,OH) in which the contents of the braces constitutes the
unit cell, M is an alkali metal cation, an alkaline earth metal
cation, an ammonium ion, or mixtures of such ions, y Mg (O,OH) is
the variable amount of accessory phase occluded therewith, and x,
y, a, and z have values within the following ranges: 0.1 .ltoreq. x
.ltoreq. 1.5 0.1 .ltoreq. y .ltoreq. 2 0 .ltoreq. a .ltoreq. 2 1
.ltoreq. z .ltoreq. 2.
Inventors: |
Granquist; William T. (Houston,
TX) |
Assignee: |
N L Industries, Inc. (New York,
NY)
|
Family
ID: |
22975718 |
Appl.
No.: |
05/257,303 |
Filed: |
May 26, 1972 |
Current U.S.
Class: |
516/110;
106/31.13; 106/286.2; 106/287.17; 106/287.27; 106/468; 252/179;
423/328.2; 424/49; 424/52; 502/410; 507/140; 514/770 |
Current CPC
Class: |
C09D
7/43 (20180101); A61Q 19/00 (20130101); B01J
29/049 (20130101); C12H 1/0408 (20130101); C01B
33/28 (20130101); B01J 21/16 (20130101); B01J
29/04 (20130101); D21H 19/40 (20130101); C01B
33/44 (20130101); A61K 8/26 (20130101); D21H
19/10 (20130101); A61Q 11/00 (20130101); B01J
2229/42 (20130101); C08K 3/34 (20130101) |
Current International
Class: |
C12H
1/00 (20060101); C09D 7/00 (20060101); C12H
1/044 (20060101); A61K 8/26 (20060101); A61K
8/19 (20060101); B01J 21/00 (20060101); B01J
21/16 (20060101); D21H 19/10 (20060101); B01J
29/04 (20060101); B01J 29/00 (20060101); A61Q
19/00 (20060101); A61Q 11/00 (20060101); D21H
19/40 (20060101); D21H 19/00 (20060101); C01B
33/00 (20060101); C01B 33/44 (20060101); B01j
013/00 () |
Field of
Search: |
;252/317,179,455Z
;423/328,329 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
bragg et al.: "Crystal Structures of Minerals," London 1965, pages
346-349; 352-353. .
Meier: page 17 of article entitled "Zeolite Structures," in
Molecular Sieves, Papers of Conference in London on Apr. 4-6, 1967;
Society of Chemical Industry, London, 1968. .
Deer et al.: "Rock Forming Minerals," Vol. 3, Sheet Silicates,
London 1962, pages 170-171; 226-227..
|
Primary Examiner: Lovering; Richard D.
Attorney, Agent or Firm: Larsen; Delmar H. House; Roy F.
Floersheimer; Fred
Claims
Having described the invention, I claim:
1. A synthetic mineral composition having the following formula per
unit cell:
{[Mg.sub.6 Al.sub.x Si.sub.8.sub.-x O.sub.20 (OH.sub.4.sub.-a
F.sub.a)].sup.x.sup.-. (xM.sup.z /z)}+y Mg (O,OH)
in which the contents of the braces constitutes said unit cell of a
smectite and in which the contents of the square brackets
represents the fixed lattice portion of the unit cell, said fixed
lattice portion having a negative charge; and in which M represents
cations balancing said negative charge, and wherein z is the
valence of said M, and in which said M is selected from the group
of cations consisting of alkali metal cations, alkaline earth metal
cations, ammonium ions, and mixtures thereof; and in which y Mg
(O,OH) is an accessory phase occluded with said smectite and
consisting of hydrous magnesium oxide selected from the class
consisting of magnesium oxide, magnesium hydroxide, hydrous
magnesium oxide species intermediate therebetween, and mixtures
thereof; and in which said x, said y, said z, and said a have
values within the following ranges:
0.1 .ltoreq. x .ltoreq. 1.5
0.1 .ltoreq. y .ltoreq. 2
0 .ltoreq. a .ltoreq. 2
1 .ltoreq. z .ltoreq. 2.
2. A mineral composition in accordance with claim 1 wherein said x
is approximately equal to 0.5, said y is approximately equal to 1,
and said a is 0.
3. A mineral composition in accordance with claim 1 wherein said M
is an alkali metal cation.
4. A mineral composition in accordance with claim 2 wherein said M
is an alkali metal cation.
5. A mineral composition in accordance with claim 3 in which said
alkali metal cation is sodium.
6. A mineral composition in accordance with claim 4 in which said
alkali metal cation is sodium.
7. A process of preparing a synthetic smectite mineral composition
which comprises the steps of forming an aqueous slurry containing
mixed hydrous oxides of silicon, aluminum, magnesium, and M and
fluoride in the proportions defined in accordance with claim 1 and
the preselected values of the variables in said claim 1 by adding
said components to water;
heating said slurry under autoclave conditions under autogenous
temperature within the range of approximately 100.degree.C to
325.degree.C. for a sufficient period of time for the mineral
composition defined by claim 1 to form;
cooling said mixture;
and recovering said mineral composition therefrom.
8. A process in accordance with claim 7 wherein said x is
approximately equal to 0.5, said y is approximately equal to 1, and
said a is equal to 0.
9. The process in accordance with claim 7 wherein said M is
sodium.
10. The process in accordance with claim 7 wherein said slurry is
maintained at room temperature for at least 8 hours before said
heating.
11. The process in accordance with claim 8 wherein said slurry is
maintained at room temperature for at least 8 hours before said
heating.
12. The process in accordance with claim 9 wherein said slurry is
maintained at room temperature for at least 8 hours before said
heating.
13. The process of increasing the consistency of an aqueous system
which comprises the step of adding to said system a quantity of the
mineral composition of claim 1 sufficient to substantially increase
said consistency.
14. The process of increasing the consistency of an aqueous system
which comprises the step of adding to said system a quantity of the
mineral composition of claim 3 sufficient to substantially increase
said consistency.
15. A composition of matter consisting essentially of an aqueous
phase and an amount of the mineral composition of claim 1
sufficient to impart a gel strength to said composition of matter
greater than in the absence of said mineral composition.
16. A composition of matter consisting essentially of an aqueous
phase and an amount of the mineral composition of claim 3
sufficient to impart a gel strength to said composition of matter
greater than in the absence of said mineral composition.
Description
This invention relates to synthetic magnesian aluminosilicates, and
more particularly to saponite-like compositions including accessory
magnesium oxide and/or hydroxide, and still more particularly to
highly swelling products obtained in accordance with the
invention.
Among clays generally, a special group of clay types exists, which
are characterized by swelling behavior in water. This group is in
contrast to the clays used for thousands of years for ceramic
purposes, in which swelling is a disadvantage since it leads to
excessive shrinkage in the production of ceramic articles. This
swelling group is characterized by a flat crystal habit in which
the equilibrium distance between the individual flat crystallites
is dependent upon the water content as well as other influences
such as the electrolyte content of the water in contact with the
clay. The term "smectite" has been revived in recent years to
embrace the so-called montmorillonite group of clays which includes
such well known members as montmorillonite, beidellite, nontronite,
saponite, hectorite, and sauconite. A discussion and further
details on smectites may be found in the book "Rock Forming
Minerals," Volume 3, Sheet Silicates, by W. A. Deer et al., London
1962, pages 226-245.
Of the smectites, montmorillonite has been widely employed since
about the turn of the century in the form of naturally occurring
bentonite, for those properties which it possesses as a result of
its ability to swell and gel in water. Another member of the group,
hectorite, has been employed as widely as its relative rare
occurrence permits, for many of the same uses as for
montmorillonite, in which it generally is preferable because of its
greater swelling behavior and white color. Because the smectites
have inherently negatively charged crystal lattices and therefore
have charge-balancing cations in positions subject to exchange by
other cations, an entire technology has arisen in the last 25 years
or so in which organic cations are employed exchanged upon
smectites, particularly montmorillonite and hectorite, to obtain
products which are swellable in organic solvents, the so-called
organophilic bentonites and organophilic hectorites.
With the high and varied utility of the smectites, it is not
surprising that some of them have been successfully synthesized on
a commercial scale, particularly hectorite. For some uses the
considerably higher cost of the synthetic products as compared with
the natural is not a bar to their economic useage.
One disadvantage possessed by smectites generally is that their
ability to swell in water is sharply reduced by the presence of
electrolytes dissolved therein. Typical results showing the effect
of various electrolytes such as sodium chloride, magnesium sulfate,
and others, may be found in the classical paper, "The Swelling of
Bentonite and Its Control" by C. W. Davis, Industrial and
Engineering Chemistry 19, 1,350-1,352 (1927).
An object of the present invention is to provide a novel product
and a process for producing the said product, which is a smectite
composition akin to saponite containing intimately admixed and
occluded hydrous magnesium oxide, the said products having
extraordinary swelling behavior in water and in aqueous electrolyte
solutions, and having wide utility generally.
Other objects of the invention will appear as the description
thereof proceeds.
Generally speaking, and in accordance with illustrative embodiments
of the invention, I provide a saponite-like mineral composition
having the following formula per unit cell:
{[Mg.sub.6 Al.sub.x Si.sub.8.sub.-x O.sub.20 (OH.sub.4.sub.- a
F.sub.a)].sup.x.sup.-. (xM.sup.z /z)} + y Mg (O,OH)
and in which the contents of the braces constitutes the unit cell
of the saponite-like mineral and y Mg (O,OH) is the variable amount
of accessory phase occluded therewith and which as the formula
indicates is magnesium oxide or magnesium hydroxide or any of the
hydrous magnesium oxide species and mixtures thereof intermediate
between these two end members. The compositional variables, x, y,
and a, may assume any value within the following limits:
0.1 .ltoreq. x .ltoreq. 1.5
0.1 .ltoreq. y .ltoreq. 2
0 .ltoreq. a .ltoreq. 2
with the preferred values being close to x equals 0.5, y equals 1,
and a equals zero. M is the charge-balancing cation, as explained
hereinbelow, having a valence of z, and is most conveniently and
preferably sodium ion, but may also be any other alkali metal or
alkaline earth metal cation or ammonium ion or substituted ammonium
ion, such as tetraethyl ammonium; or mixtures thereof. It will be
clear that if a mixture is present in which the ions M have
different valences, then z will be an average value for the
mixture. Further, the contents of the square brackets represents
the fixed lattice portion of the unit cell, which as will be seen
from totalling up the positive and negative charges of the ions
contained in this lattice and shown in the square brackets, is
negative. The charge-balancing positive charges are shown, outside
of the square brackets but within the braces, and as will be seen
from the above formulation, these charge-balancing cations are
represented by M. Furthermore, the hydrous magnesium oxide
accessory phase, as will be explained in more detail hereinbelow,
is not merely admixed with a previously formed saponite-like phase,
but is present in the synthesis reaction mixture so that it is
present at the time the crystal lattice within the square brackets
is formed, and is thus intimately associated therewith, for which
the term occluded therewith is fitting.
In order to prepare the novel products in accordance with the
invention, an aqueous reaction mixture in the form of an aqueous
slurry is prepared containing mixed hydrous oxides of silicon,
aluminum, and magnesium, and sodium (or alternate cation or mixture
thereof) hydroxide with or without, as the case may be, sodium (or
alternate cation or mixture thereof) fluoride in the proportions
defined by the above formula and the preselected values of x, y,
and a for the particular product desired. Optionally, but
preferably, the slurry is allowed to age for at least 8 hours at
room temperature after having been formed. The slurry is then
placed in an autoclave and heated under autogenous pressure to a
temperature within the range of approximately 100.degree. to
325.degree.C. and preferably about 300.degree.C. for a sufficient
period of time for the inventive product to form by the
hydrothermal synthesis thus brought about. Formation times of 3 to
5 hours are typical, and the optimum time for a given preparation
can readily be determined by pilot trials. After the synthesis is
complete, then the autoclave and contents are permitted to cool to
room temperature and the contents removed. In general, no washing
of the product is necessary, but the entire contents may simply be
spray dried or otherwise dried and ground if desired.
When a is selected to be zero, so that fluorides are not present, a
convenient way to add the required amounts of alumina and sodium
hydroxide is in the form of sodium aluminate, NaAlO.sub.2. This
results in the number of aluminum ions added to the system being
accompanied by the same number of sodium ions, which I find
preferable. However, satisfactory products are likewise obtained
when the number of aluminum ions exceeds the number of sodium ions
or equivalent selected cation or mixture of cations, such as
potassium, lithium, calcium, ammonium, and the like.
Some specific examples will now be given, together with a
tabulation of some of the properties of the products obtained.
EXAMPLE I
To A pounds of SiO.sub.2, as a polysilicic acid sol prepared from
Na-silicate solution by the teachings of U.S. Pat. No. 3,649,556,
were added a solution of B pounds of sodium aluminate (Na.sub.2 O.
Al.sub.2 O.sub.3. 3 H.sub.2 O) dissolved in a minimum amount of
water, and C pounds of calcined magnesite (assaying 92.7% MgO) as a
slurry prepared by shearing the MgO with water on a Cowles
Dissolver. The amount of water was adjusted to give 7% solids and
this feed slurry was aged in the feed mix tank, with stirring, for
20 hours. After such aging, the slurry was diluted to 4% solids and
then pumped to a 140-gallon autoclave. Hydrothermal treatment was
at 300.degree.C. and 1,240 psig for 4 hours; the time for the
autoclave to be heated from room temperature to 300.degree.C. was
121/2 hours. The product slurry was discharged from the autoclave
through a quench condenser and then spray-dried.
For several runs, the values of A, B, and C, and of the parameters
x, y, and a are given in Table 1.
Table 1 ______________________________________ Sample A B C x y a
______________________________________ 1-1 20 11.58 2.42 0.5 0 0
1-2 15 9.41 1.81 0.5 0.5 0 1-3 13.2 8.92 1.60 0.5 1.0 0 1-4 13.2
9.57 1.60 0.5 1.5 0 ______________________________________
Some rheological properties of 2.5% (dry basis) dispersions in
water and in salt solution of the products described in Table 1 are
listed in Table 2. The viscometer used was a Fann V-G meter (See
Savins, U.S. Pat. No. 2,703,006 for design and theory).
Table 2 ______________________________________ Plastic Vis., Yield
Strength cp. 24 hr. .andgate./100 ft.sup.2
______________________________________ Dist. Sat. NaCl Dist. Sat.
NaCl Sample Y H.sub.2 O soln. H.sub.2 O soln.
______________________________________ 1-1 0 2 2 0.5 0 1-2 0.5 1.5
7.5 4.5 3.5 1-3 1.0 1.5 8.0 9.0 36.5 1-4 1.5 2.0 2.5 8.5 15.0
______________________________________
Note that when y equals zero, unsatisfactory rheological properties
are obtained, and indeed, this preparation (Sample 1--1) is outside
the scope of the invention.
EXAMPLE II
Plant-scale synthesis was accomplished from a polysilicic acid sol
as described in Example I, hammer-milled calcined magnesite,
alumina trihydrate, and liquid caustic (50% NaOH). The magnesite
was sheared in tap water by means of a Cowles Dissolver, and the
resulting slurry added with agitation to the polysilicic acid sol.
The proper amounts of alumina trihydrate and caustic were then
added, again with agitation. The feed slurry thus prepared was aged
about 48 hours (over a weekend), then diluted with water to 4%
solids. The feed composition thus obtained can be described by the
following molar ratios:
SiO.sub.2 /MgO = 1.088; SiO.sub.2 /Al.sub.2 O.sub.3 = 19.7;
SiO.sub.2 /NaOH = 15.0;
the pH was 10.25. It will be noted from these ratios that the
composition contained some excess alumina.
The feed was pumped into an autoclave through a preheater, and
attained in this way a temperature of 150.degree.C. at entry to the
autoclave. In the autoclave the temperature was increased to
300.degree.C. and the pressure correspondingly increased to 1,240
psig. The autoclave was maintained at these latter conditions for 3
to 4 hours and then discharged through a quench condenser. The
product slurry was spray-dried.
The product so obtained had the properties listed in Table 3.
Table 3 ______________________________________ A. General
Properties ______________________________________ Moisture,
105.degree.C. % 8.99 Ignition Loss, 900.degree.C., % (dry basis)
8.97 Bulk density, lb/ft.sup.3 Uncompacted 61.5 Compacted 68.6
Cation exchange capacity, meq/100 gm NH.sub.4 Ac method 56
Methylene blue method 80 Calculated from composition 65 Oil
Absorption, ASTM C.281-31, lb/100 lb 50 pH value (4% solids in
water) 10 ______________________________________
Table 4 ______________________________________ B. Viscosity
Data(Fresh Water),3.3% solids, Fann V--G meter Shear Stress (dial
deflection) Shear Rate, rpm Initial 24 hour
______________________________________ 600 30 38 300 28 33 200 26
31 100 24 29 6 20 22 3 20 22 Initial 24 hour Plastic viscosity,
centipoise 2 5 Yield point, lb/100 ft.sup.2 26 28 10 sec. gel
strength, lb/100 ft.sup.2 42 38 10 min. gel strength, lb/100
ft.sup.2 102 75 ______________________________________
Table 5 ______________________________________ C. Viscosity Data
(Electrolyte Solutions), Initial Test, Fann V--G meter lb/100
Ft.sup.2 Plastic Yield 10 sec. 10 min Fluid %Solids Viscosity,
Point Gel Gel cp Strength Strength
______________________________________ Fresh 3 2 26 42 102 Water
Sea 6 7 41 37 55 Water Sat. 3.85 7 40 34 45 NaCl Sat. 3.85 10 29 19
28 CaCl.sub.2 lN NaOH 4 5 10 9 10
______________________________________
The data in Tables 4 and 5 establish the unique gelling properties
of this synthetic product. The plastic viscosity is low but the gel
strength and yield point are high for a variety of suspending
fluids. It is apparent from these rheological data that this
product is a useful gellant for fluids as varied as fresh water,
sea water, saturated sodium chloride and calcium chloride
solutions, and 1N NaOH.
The data on cation exchange capacity in Table 3 include the
methylene blue method result, although this is not reliable in this
instance. The agreement between the calculated figure and the
ammonium acetate determination is satisfactory.
EXAMPLE III
Another sample of product made as described for Example II was
converted to the ammonium form by repeated leaching with ammonium
acetate solution. It was washed, and calcined at 700.degree.C. for
4 hours. Its ability to crack cumene was determined by saturating
helium with cumene at 55.degree.C. and then passing it over a 0.25
g sample of the calcined material, ground to 30/60 mesh. The
reactor temperature was 350.degree.C., and the flow rate was 1 cc
per second. After one hour of continuous flow, a sampling of the
output showed a conversion rate of 59.3% of the cumene to propylene
and benzene.
The calcined product had a specific surface area of 307 square
meters per gram, as determined by the Brunauer-Emmett-Teller method
using nitrogn as the adsorbate.
EXAMPLE IV
81.2 g of hammermilled calcined magnesite assaying 92.7% MgO were
added to water and sheared in a laboratory mixer (a Cowles
Dissolver) to obtain good dispersion of the particles. This slurry
was added with agitation to 120 g of silica in the form of a
polysilicic acid sol containing 5.7% SiO.sub.2. To this mixture
there were added with stirring 10.5 g of alumina trihydrate (64.9%
Al.sub.2 O.sub.3), and 11.5 g of NaF which had been dissolved in a
minimum of water. The volume at this stage was 2.2 liters, all of
which was charged into a 1-gallon stirred autoclave. The autoclave
and contents were heated to 300.degree.C. at which temperature the
pressure was 1,240 psi gage. The heating time to final temperature
was 1 hour, 45 minutes. The autoclave was maintained at
300.degree.C. for 4 hours. The vessel was then cooled, the product
slurry removed, dried at 105.degree.C., and ground. X-ray
diffraction indicated good crystallinity with MgO as the only
accessory phase. The unit cell formula for the product was
approximately as follows:
{Mg.sub.6 Si.sub.7.5 Al.sub.0.5 O.sub.20 (OH).sub.3 F .sup.. 0.5
Na} + 1 MgO
The solids content of the slurry when placed into the autoclave is
not critical. Less than about 2% solids is wasteful from the
standpoint of heating losses and throughput for a given piece of
equipment, and in addition, synthesis times may be somewhat
prolonged. On the other hand, greater than about 10% solids
generally results in a slurry which cannot conveniently be handled
by ordinary equipment. I prefer from about 3% to about 5% solids in
the slurry, as illustrated in the examples given.
The inventive products, as already indicated, have wide utility.
Particularly in the case of those inventive products in which M is
univalent, and more particularly when M is largely sodium or
lithium or a mixture thereof, the ability to spontaneously disperse
and swell in water makes them useful for drilling mud additives; as
thickeners and thixotropy imparting agents for water base paints;
as thickeners and bodying agents for aqueous cosmetic preparations,
dentifrices such as toothpaste, and the like. The large surface
area developed upon dispersion in aqueous liquids makes them highly
useful for the clarification of beer, wine, vinegar, and honey.
Their ability to coat paper with a thin adherent film makes them
useful in the paper sizing art generally, and in particular their
cation exchange capacity in combination with their surface
catalytic properties especially for certain organic amines renders
them especially useful in those copying papers wherein pressure
releases microencapsulated color-forming agents, as set forth, for
example, in British Pat. No. 773,180.
The cation-exchange capacity also makes possible the conversion of
the inventive products to organophilic smectites, for which the
general procedures set forth in Hauser U.S. Pat. No. 2,531,427, the
contents of which are incorporated herein by reference, may be
employed. Such organophilic smectites in turn have wide utility;
they may be used in the formulation of lubricating greases, as set
forth in Jordan U.S. Pat. No. 2,531,440; in paints, varnishes and
printing inks, as set forth in Ratcliffe U.S. Pat. No. 2,622,987
and the like. The aforesaid Jordan and Ratcliffe patents are
likewise incorporated herein by reference.
The inventive products have wide catalytic utility, such as for
cracking hydrocarbons, for reforming hydrocarbons, in various
organic reactions in which clay catalysts have heretofore been
used, and as active carriers for other catalytic substances such as
platinum, palladium, nickel, cobalt, molybdenum, copper, and other
heavy metals, in their cationic, metallic, or oxide or sulfide or
other combined form.
While my invention has been described with the aid of numerous
specific examples, it will be recognized by those skilled in the
art that many variations are possible without departing from the
spirit and scope of the invention.
It will be clear from all of the foregoing, and in particular from
the examples, that my synthetic mineral composition may be used
with great advantage whenever it is desired to increase the
consistency of an aqueous system, including compositions generally
having an aqueous phase. The increase in consistency may be
followed by any of the known rheological methods, one of the
simplest and most direct of which is the determination of the gel
strength. The consistency-increasing properties of my inventive
products are especially marked in those in which the exchangeable
cation is an alkali metal cation. In general, simple addition of
the inventive product to the system suffices, followed when desired
or indicated by stirring or like agitation.
* * * * *